3-Alkylated-5,5&#39;,6,6&#39;,7,7,&#39;8,8&#39;-octahydro-2,2&#39;-binaphthols and 3,3&#39;-dialkylated-5,5&#39;,6,6&#39;,7,7&#39;,8,8&#39;-octahydro-2,2&#39;-binaphthols and processes for making them

ABSTRACT

The compositions 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and 3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol are disclosed, as well as various processes for making them, all involving the alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol.

FIELD OF THE INVENTION

[0001] This invention relates to the compositions3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and certain3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and toprocesses for making 3-alkylated-, and3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols,generally.

BACKGROUND OF THE INVENTION

[0002] Phosphorous-based ligands are useful as part of the catalystsystem in industrially important reactions such as hydroformylation andhydrocyanation. The useful ligands include phosphines, phosphinites,phosphonites, and phosphites. See PCT patent applications WO 99/06146and WO 99/62855. Both mono(phosphorous) ligands and bis(phosphorous)ligands are utilized in the art. Mono(phosphorous) ligands are compoundsthat contain a single phosphorus atom which serves as a donor to atransition metal, while bis(phosphorus) ligands, in general, contain twophosphorus donor atoms and typically form cyclic chelate structures withtransition metals.

[0003] Processes for the preparation of3,3′-dialkyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols, unliketheir 3-alkyl-5,5′,6,6′,7,7′, 8,8′-octahydro-2,2′-binaphthol analogs,appear in the literature. One such process, disclosed in J. Chem. Soc.,C 1971, 23, teaches the preparation of3,3′-di-t-butyl-5,5′,6,6′,7,7′8,8′-octahydro-2,2′-binaphthols by thecoupling of 3-t-butyl-5,6,7,8-tetrahydro-2-naphthol using potassiumferricyanide and FeCl₃-based methods with yields of only 25% and 6%,respectively. Also disclosed is the coupling of3-t-butyl-5,6,7,8-tetrahydro-2-naphthol to give3,3′-di-t-butyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol can becarried out with a large excess MnO₂ (20 times in weight).

[0004] Another process, disclosed in Acta Chem. Scand. 1970, 24, 580,teaches the coupling of 3,4-dimethyl-5,6,7,8-tetrahydro-2-naphthol togive 3,3′,4,4′-tetramethyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith 43% yield. J. Org. Chem. 1978, 43, 1930 discloses the preparationof 3,3′-dimethyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol by LiAlH₄reduction of3,3′-di(bromomethyl)-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol.

[0005] There has been no report in the prior art regarding acidcatalyzed alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol toproduce 3-alkyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols or3,3′-dialkyl-5,5′,6,6′,7,7′8,8′-octahydro-2,2′-binaphthols. Acidcatalyzed alkylation of phenols is known. For example, U.S. Pat. No.4,912,264 discloses heteropoly acid catalyzed phenol and naphtholalkylation. U.S. Pat. No. 2,733,274 discloses cresol sulfonic acidcatalyzed phenol alkylation. J. Am. Chem. Soc., 1945, 67, 303 disclosesaluminum chloride catalyzed phenol alkylation. Industrial andEngineering Chem., 1943, 35, 264 discloses sulfuric acid catalyzedphenol alkylation. Friedel-Crafts alkylation of aromatic compounds hasalso been reviewed. For example, see Olah, G. A. Friedel-Crafts andRelated Reactions, Wiley-Interscience: New York, 1964, Vol. II, part I,Roberts, R. Friedel-Crafts Alkylation Chemistry, Marcel Dekker, 1984,and March, J. Advanced Organic Chemistry, 4^(th) Edition,Wiley-Interscience: New York, 1992, pp 534-539.

[0006] Recently, it was disclosed that rare earth metaltrifluoromethanesulfonates as water-tolerant Lewis acid catalysts can beutilized in Friedel-Crafts alkylation of benzene and phenol derivativeswith secondary alkyl methanesulfonates. See SynLett, 1998, 255-256 andSynthesis, 1999, 603-606.

[0007] It is not practical to use LiAlH₄, a large excess of MnO₂, oreven a stoichiometric amount of potassium ferricyanide to carry outindustrial scale preparations of alkylated, hydrogenated binaphthols.Such a process would be expected to generate a large amount ofbyproducts. Therefore, a need exists in the art for a practical andgeneral method to prepare3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols.

SUMMARY OF THE INVENTION

[0008] In its composition of matter aspect, the present inventionprovides 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols ofthe formula (1) and 3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols of the formula (2).

[0009] R is C₁ to C₂₀ alkyl, C₃ to C₂₀ cycloalkyl, or benzyl of theformula

[0010] wherein each R′ is independently H, alkyl or cycloalkyl of up to6 carbons; provided that in formula (2), when R is alkyl, the alkyl mustbe other than methyl or t-butyl.

[0011] In its first process aspect, the present invention provides aprocess for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols bycontacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with an alkeneor cycloalkene in the presence of an acid catalyst such as aluminumchloride, trifluoromethanesulfonic acid, tosylic acid, phosphotungsticacid, silicotungstic acid, phosphomolybdic acid, zirconium or aluminumtriflate, polymeric perfluorinated sulfonic acid (such as the DuPontmaterial sold as Nafion®) and polymeric sulfonic acid (such as thematerial sold by Aldrich as Amberlyst® 15 ion-exchange resin or thematerial sold by Dow as Dowex 32®).

[0012] In its second process aspect, the present invention provides aprocess for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols bycontacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with benzylhalides or tertiary alkyl halides in the presence of a Lewis acidcatalyst, such as aluminum chloride or zinc chloride.

[0013] In its third process aspect, the present invention provides aprocess for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols bycontacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with alkylsulfonates, fluorinated alkyl sulfonates, alkyl benzenesulfonates, oralkyl p-toluenesulfonates in the presence of an acid catalyst such astrifluoromethanesulfonic acid or scandium triflate.

[0014] In its fourth process aspect, the present invention provides aprocess for making 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols and 3,3′-dialkylated-5,5′, 6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols by contacting5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with benzyl alcohol, orsecondary or tertiary alcohol in the presence of aluminum chloride,trifluoromethanesulfonic acid, tosylic acid, phosphotungstic acid,silicotungstic acid, phosphomolybdic acid, zirconium or aluminumtriflate, polymeric perfluorinated sulfonic acid (such as Nafion®) orpolymeric sulfonic acid.

[0015] In another aspect, the present invention is a compound of theformula

[0016] wherein:

[0017] R is H; and

[0018] R′ is ethyl, C₃ to C₆ secondary, tertiary, or cyclic alkyl;

[0019] or a compound of the above formula wherein

[0020] R and R′ are the same and are selected from the group consistingof

[0021] ethyl, C₃ to C₆ secondary or cyclic alkyl.

[0022] Preferred compounds are those wherein R and R′ are the same areselected from the group consisting of ethyl, isopropyl, cyclopentyl, andcyclohexyl.

DETAILED DESCRIPTION OF THE INVENTION

[0023] The alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols ofthis invention may be prepared by alkylation of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol in the presence of acatalyst, as shown below.

[0024] The starting material,5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, can be obtained by thehydrogenation of 2,2′-binaphthol using a PtO₂ catalyst, as described inTetrahedron Lett. 1997, 5273.

[0025] The first process aspect of the present invention is a processfor making alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols byan acid-catalyzed, selective alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol by alkenes or cycloalkenes inthe presence of an acid catalyst. The acid catalyst may be a Lewis acidor a protic acid. Suitable catalysts include the following: AlCl₃,trifluoromethanesulfonic acid, tosylic acid, phosphotungstic acid,silicotungstic acid, phosphomolybdic acid, zirconium or aluminumtriflate, polymeric perfluorinated sulfonic acid (such as the materialsold by DuPont as Nafion®) and polymeric sulfonic acid (such as thematerial sold by Aldrich as Amberlyst® 15 ion-exchange resin or thematerial sold by Dow as Dowex 32®). Phosphotungstic acid is preferred.The alkenes include monoethylenically unsaturated compounds containingfrom 3 to 20 carbons, such as propylene, butene, pentene, hexene,cyclopentene, cyclohexene, etc. The reaction may be carried out at 20°C. to 220° C., preferably at 90° C. to 180° C., when mono-substituted or1,2-disubstituted alkenes are utilized as alkylating reagents, and 40°C. to 90° C. when 1,1-disubstituted, tri-substituted, tetra-substitutedor aryl-substituted alkenes are utilized as alkylating reagents. Thealkylation reaction may be carried out neat (without solvent) or ininert solvents such as nitromethane, methylene chloride, dichloroethane,chlorobenzene, dichlorobenzene, nitrobenzene or a combination of thesesolvents. Other solvents such as benzene, toluene, and xylene may alsobe used, but the solvents may become alkylated. When the boiling pointof the alkene is lower than the reaction temperature, the reaction maybe carried out in an autoclave or by feeding the alkene at atmospherepressure. The reaction may be carried out in an autoclave when theboiling point of the solvent(s) is lower than the reaction temperature.A large excess of alkene over binaphthol gives double alkylated5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, while about twoequivalents or less of alkene (relative to5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol) gives both mono anddouble alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols.

[0026] The second process aspect of the present invention is a processfor making alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol bythe reaction of 5,5′, 6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol withbenzyl halide or tertiary alkyl halide in the presence of a Lewis acidcatalyst. Suitable catalysts include the following: aluminum chloride,zinc chloride, boron trichloride, SnCl₄, SbCl₅, and ZrCl₄. Zinc chlorideis preferred. Suitable halides are bromides and chlorides. The reactionmay be carried out at 0° C. to 100° C., preferably at 20° C. to 80° C.The alkylation reaction may be carried out in inert solvents such asnitromethane, methylene chloride, dichloroethane, chlorobenzene,dichlorobenzene, nitrobenzene or a combination of these solvents. Othersolvents such as benzene, toluene, and xylene may also be used, but thesolvents may become alkylated. When tertiary alkyl halide is used as analkylating reagent, the reaction is very selective towardsmono-alkylated 5,5′, 6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol even whenseveral equivalents excess of tertiary alkyl halide are used. However,double alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholeventually is formed when a large excess of tertiary alkyl halide isused and the reaction is allowed to run at higher temperature and forlonger time. When benzyl halide is used as an alkylating reagent, doublebenzylated 5,5′,6,6′,7,7′, 8,8′-octahydro-2,2′-binaphthol is formed whena large excess of benzyl halide relative to binaphthol is used, whileone equivalent of the benzyl halide (relative to5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol) gives predominantlymono-benzylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols.

[0027] The third process aspect of the present invention is a processfor making alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol bythe reaction of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with alkylsulfonates such as alkyl methanesulfonates, alkyl triflates, alkylp-toluenesulfonates, and alkyl benzenesulfonates in the presence of anacid catalyst. Suitable alkyl sulfonates are of the formula A-SO₃—B,wherein A is C₁ to C₈ alkyl, C₁ to C₈ fluorinated alkyl, C₆ to C₁₀ aryl,or C₆ to C₁₀ fluorinated aryl; and B is C₁ to C₂₀ alkyl. Suitablecatalysts for alkylation of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with alkyl sulfonatesinclude Lewis acids such as aluminum chloride and boron trifluoride, aswell as other acid catalysts such trifluoromethanesulfonic acid, tosylicacid, and rare earth metal triflates such as scandiumtrifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, orlanthanum trifluoromethanesulfonate. Trifluoromethanesulfonic acid andscandium trifluoromethanesulfonate are the preferred catalysts.Alkylation of 5,5′,6,6′,7,7′, 8,8′-octahydro-2,2′-binaphthol may becarried out at 20° C. to 220° C., preferably at 90° C. to 180° C. Thealkylation reaction may be carried out in inert solvents such asnitromethane, methylene chloride, carbon tetrachloride, dichloroethane,chlorobenzene, dichlorobenzene, nitrobenzene or a combination of thesesolvents. Other solvents such as benzene, toluene, and xylene may alsobe used, but the solvents may become alkylated. The product of thereaction of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with alkylsulfonates varies depending on stoichometry and alkylation reagent used.A large excess of alkyl sulfonate gives double alkylated5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, while about 1.5equivalents or less of alkyl sulfonate (relative to5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol) gives predominately monoalkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols.

[0028] The fourth process aspect of the present invention is a processfor making alkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol bythe reaction of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol withbenzyl alcohol, secondary and tertiary alcohols containing 3 to 20carbon atoms, in the presence of an acid catalyst. Suitable catalystsinclude the following: trifluoromethanesulfonic acid, tosylic acid,aluminum chloride, phosphotungstic acid, silicotungstic acid,phosphomolybdic acid, polymeric perfluorinated sulfonic acid (such asNafion®) and polymeric sulfonic acid (such as Amberlyst®15 ion-exchangeresin and Dowex 32®). Trifluoromethanesulfonic acid is preferred.Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol withalcohols may be carried out at 20° C. to 220° C., preferably at 90° C.to 180° C. The alkylation reaction may be carried out in inert solventssuch as nitromethane, methylene chloride, carbon tetrachloride,dichloroethane, chlorobenzene, dichlorobenzene, nitrobenzene or acombination of these solvents. Other solvents such as benzene, toluene,and xylene may also be used, but the solvents may become alkylated. Theproduct of the reaction of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith alcohol varies depending on stoichometry and alkylation reagentused. When tertiary alcohol is used as the alkylating agent, monoalkylated 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthols were obtainedpredominantly, even when several equivalents excess of tertiary alcoholwas applied. A large excess of the secondary alcohol (relative to5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol) gave rise to both monoand double alkylated products.

[0029] Catalysts used in the processes of the present invention may beunsupported or supported. Suitable supports include silicon dioxide,zeolites, alumino silicates, and polystyrene.

[0030] The compounds which are produced by the process of the presentinvention can be used as reactants to make phosphorous-containingligands that are useful to make catalysts that, in turn, are useful inboth hydrocyanation and hydroformylation reactions. Bidentate phosphiteligands are particularly useful.

[0031] Bidentate phosphite ligands can be prepared as described in U.S.Pat. No. 5,235,113 by contacting phosphorochloridites with the compoundsmade by the processes of the present invention. More recent U.S. Pat.Nos. 6,031,120 and 6,069,267, incorporated herein by reference, describeselective synthesis of bidentate phosphite ligands in which aphosphorochloridite is prepared in-situ from phosphorus trichloride anda phenol such as o-cresol and then treated in the same reaction vesselwith an aromatic diol to give the bidentate phosphite ligand. Thealkylated products of the processes of the present invention can besubstituted for the aromatic diol in the above process.

[0032] The compounds made by the processes of the present invention canbe used to make polymeric ligands by a process which comprises (1)reacting the compounds made by the processes of the present inventionwith a benzyl chloride containing polymer, in the presence of a Lewisacid catalyst, and (2) reacting the product of step (1) with at leastone phosphorochloridite compound in the presence of an organic base.Preferably the Lewis acid catalyst is zinc chloride or aluminumchloride, and the organic base is a trialkylamine.

[0033] Two particularly important industrial catalytic reactions usingphosphorus-containing ligands are olefin hydrocyanation andisomerization of branched nitrites to linear nitrites. Phosphite ligandsare particularly useful for both reactions. The hydrocyanation ofunactivated and activated ethylenically unsaturated compounds (olefins)using transition metal complexes with monodentate and bidentatephosphite ligands is well known. Bidentate phosphinite and phosphoniteligands are useful as part of a catalyst system for the hydrocyanationof ethylenically unsaturated compounds. Bidentate phosphinite ligandsare also useful as part of a catalyst system for the hydrocyanation ofaromatic vinyl compounds.

[0034] Hydroformylation is another industrially useful process thatutilizes catalysts made from phosphorus-containing ligands. The use ofphosphine ligands, including diphosphines, is known for this purpose.The use of catalysts made from phosphite ligands is also known. Suchcatalysts usually contain a Group VIII metal. See for example, U.S. Pat.No. 5,235,113, the disclosure of which is incorporated herein byreference.

[0035] The present invention also relates to compounds of the formula

[0036] wherein:

[0037] R is H; and

[0038] R′ is ethyl, C₃ to C₆ secondary, tertiary, or cyclic alkyl;

[0039] or a compound of the above formula wherein

[0040] R and R′ are the same and are selected from the group consistingof

[0041] ethyl, C₃ to C₆ secondary or cyclic alkyl.

[0042] Preferred compounds are those wherein R and R′ are the same areselected from the group consisting of ethyl, isopropyl, cyclopentyl, andcyclohexyl.

EXAMPLES

[0043] The following non-limiting, representative examples illustratethe processes and compositions of the present invention.

Example 1 Synthesis of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol

[0044] A mixture of 5,5′,6,6′,7,7′,8,81-octahydro-2,2′-binaphthol (30.0g), xylene (5 ml) and phosphotungstic acid (1.5 g) was heated to 140° C.To the mixture was added propylene (8.9 g) slowly via a dry-icecondenser. GC analysis of the reaction mixture indicated that 98%conversion of the 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol. Smallamounts of isopropylated xylene were observed as well. The mixture waspurified by flash column to give 14.5 g of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, mp 110° C.;3.7 g of 3,3′-diisopropyl-5,5′,6,6′,7,7′8,8′-octahydro-2,2′-binaphthol,mp 152-3° C.; and a mixture (15 g) containing 38% of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and 33% of3,3′-diisopropyl-5,5′, 6,6′,7,7′8,8′-octahydro-2,2′-binaphthol.

[0045] 3-isopropyl-5,5′,6,6′,7,7′, 8,8′-octahydro-2,2′-binaphthol:

[0046]¹³C NMR (CDCl₃): 22.57, 22.63, 22.96, 23.02, 23.2, 26.9, 27.09,27.14, 29.3, 29.4, 112.9, 118.4, 119.2, 127.7, 129.5, 130.1, 131.0,132.5, 133.9, 137.2, 148.7, 151.5 ppm. ¹H NMR (CDCl₃): 1.27 (d, J=7 Hz,6H), 1.68 (m, 4H), 1.75 (m, 4H), 2.23 (m, 4H), 2.76 (m, 4H), 3.28(septet, J=7 Hz, 1H), 4.61 (s, 1H), 4.63 (s, 1H), 6.83 (s, 1H), 7.01 (s,1H), 7.08 (s, 1H) ppm.

[0047] 3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol:

[0048]¹H NMR (CDCl₃): 1.27 (d, J=7 Hz, 12H), 1.68 (m, 4H), 1.73 (m, 4H),2.17 (AB q & t, J=17, 6 Hz, 4H), 2.78 (t, J=6 Hz, 4H), 3.27 (septet, J=7Hz, 2H), 4.64 (s, 2H), 6.98 (s, 2H) ppm.

Example 2 Synthesis of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol

[0049] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol (44.0g), dichlorobenzene (10 ml) and phosphotungstic acid (2.3 g) was heatedto 130° C. To the mixture was added excess propylene via a dry-icecondenser. The reaction was monitored by GC analysis. The reactionmixture contained 6% of monoisopropylated product and 83% ofdiisopropylated product. The mixture was purified by flash column togive 20.0 g of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol.

Example 3 Synthesis of3,3′-dicyclopentyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol:

[0050] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (48 g),phosphotungstic acid (2.4 g) and cyclopentene (58 g) was charged into aHastelloy reactor. The reactor was heated to 180C for 40 hours. Themixture was purified by column chromatography (silica gel, eluting with2% ethyl acetate/hexane) to yield 29.5 g (42%) of3,3′-dicyclopentyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, mp143-152° C. ¹³C NMR (CDCl₃):22.96, 25.31, 26.68, 29.19, 32.72, 32.75,39.20, 118.58, 128.14, 129.20, 129.74, 133.91, 149.14 ppm. 1H NMR(CDCl₃): 1.60 (m, 10H), 2.0 (d, 4H), 2.65 (t, J=4 Hz, 2H), 3.27(quintet, J=7 Hz, 1H), 4.55 (s, 1H), 6.92 (s, 1H) ppm.

Example 4 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Propylene and Phosphotungstic Acid Catalyst

[0051] A solution of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight % ofphosphotungstic acid. GC analysis indicated 100% conversion of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formation of3,3′-diisopropyl-5,5,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (55%).

Example 5 Alkylation of 5,5′, 6,6′,7,7′, 8,8′-octahydro-2,2′-binaphtholwith Propylene and Amberlyst®15 Ion-Exchange Resin Catalyst

[0052] A solution of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight % ofAmberlyst®15 ion-exchange resin purchased from Aldrich (PO Box 355,Milwaukee, Wis. 53201 USA). GC analysis indicated 100% conversion of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formation of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (53%) and3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (18%).

[0053] Example 6

Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol withPropylene and Nafion®/Silica Catalyst

[0054] A solution of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight %Nafion®/silica purchased from Engelhard Corp (Nafion® SAC 13, EngelhardCorp. Beachwood, Ohio). GC analysis indicated 100% conversion of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formation of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (22%) and of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (54%).

Example 7 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Propylene and Trifluoromethanesulfonic Acid on Silica Catalyst

[0055] A solution of 5,5′, 6,6′,7,7′, 8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight %trifluoromethanesulfonic acid on silica purchased from United Catalysts(Louisville, PO Box 32370, Ky. 40232). GC analysis indicated 81%conversion of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formationof 3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (55%) and of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (25%)based on consumed 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol.

Example 8 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Propylene and Sulfated Zirconia Catalyst

[0056] A solution of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight %sulfated zirconia purchased from MEL Chemicals (XZO682/01, MELChemicals, Flemington, N.J.). GC analysis indicated 100% conversion of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formation of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (5%) and of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (77%).

Example 9 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Propylene and Dowex 32®, (Ion Exchange Resin Based on SulfonicAcids) Catalyst

[0057] A solution of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight %Dowex 32®, Dow No. 8435445, purchased from Dow Chemical (Midland, Mich.,USA). GC analysis indicated 100% conversion of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formation of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (25%) and of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (55%).

Example 10 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Propylene and Deloxin® ASP (Alkylsulfonic Acid on Silica) Catalyst

[0058] A solution of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol ino-dichlorobenzene and dodecane (24 weight % of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol, 63 weight %o-dichlorobenzene, 13 weight % dodecane) was heated to 140° C. for 3hours under 60 to 70 psi of propylene in the presence of 17 weight % ofDeloxin® ASP (alkylsulfonic acid on silica) produced by Degussa (Hanau,Deutschland). GC analysis indicated 100% conversion of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formation of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (63%) and of3,3′-diisopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (<10%).

Example 11 Alkylation of 5,5′, 6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Tertiary-Butyl Chloride and Zinc Chloride Catalyst

[0059] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (5.0g), zinc chloride (0.4 g), chloroform (5 ml), and tertiary-butylchloride (10 g) was heated to 60° C. for 4 hours. GC analysis indicated90% conversion of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol andformation of 3-t-butyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol(95%) and of 3,3′-di-t-butyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (˜2.4%) based on consumed of5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol. The mixture was purifiedby flash column chromatography to yield 4.36 g of solid. ¹H NMR (CDCl₃):1.43 (s, 9H), 1.65-1.88 (m, 8H), 2.09-2.34 (m, 4H), 2.71-2.79 (m, 4H),4.66 (s, 1H), 4.87 (s, 1H), 6.82 (d, 1H, J=8 Hz), 7.04 (d, 1H, J=8 Hz),7.10 (s, 1H) ppm. ¹³C NMR (CDCl₃): 22.9, 23.0, 23.1, 23.2, 26.8, 27.0,29.2, 29.4, 29.6, 34.5, 113.0, 119.1, 119.3, 128.2, 128.9, 130.0, 131.0,133.8, 134.2, 137.2, 149.9, 151.6 ppm.

Example 12 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Benzyl Alcohol and Trifluoromethanesulfonic Acid

[0060] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (1.5g), trifluoromethanesulfonic (61 mg), o-carbon tetrachloride (2 ml), andbenzyl alcohol (0.55 g) was heated to 80° C. for 2.5 hours. GC analysisindicated 73% conversion of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaptholand formation of 3-benzyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol(90% based on consumed of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol.To the cooled reaction mixture was added 10 mL 10% NaOH. The layers wereseparated, and the aqueous layer was extracted with ethyl aceate. Theorganic layers were combined, washed with brine, dried and concentrated.The crude material was purified by flash column chromatography (silicagel, eluting with 2% ethyl acetate/hexanes to 5% ethyl acetate/hexanes),to yield 1.13 g white solid (58% yield). ¹H NMR (CDCl₃): 1.56-1.67 (m,8H), 2.03-2.21 (m, 4H), 2.59-2.67 (m, 4H), 3.93 (s, 2H), 4.47 (s, 1H),4.56 (s, 1H), 6.72 (d, 1H, J=5 Hz), 6.79 (s, 1H), 6.96 (d, 1H, J=5 Hz),7.10-7.21 (m, 5H) ppm. ¹³C NMR (CDCl₃): 22.79, 22.87, 22.91, 26.79,26.94, 29.00, 29.07, 35.72, 112.78, 118.52, 118.90, 125.02, 125.71,128.18, 128.68, 129.62, 129.94, 130.83, 131.68, 134.76, 136.96, 140.85,149.07, 151.23 ppm.

Example 13 Alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphtholwith Benzyl Chloride and Zinc Chloride Catalyst

[0061] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (0.59g), zinc chloride (40 mg), chloroform (2 ml), and benzyl chloride(0.279) was heated to 60° C. for 4.5 hours. GC analysis indicated 70%conversion of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol and formationof 3-benzyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol (95% based onconsumed of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binapthol.

Example 14 Synthesis of3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol

[0062] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol (2 g,6.8 mmol), isopropyl methanesulfonate (5.5 mmol), scandium triflate(0.34 g, 5 mol %), and carbon tetrachloride (10 ml) was brought toreflux under argon. After 18 hours, GC indicated 65% conversion to give78% desired product. Additional isopropyl methanesulfonate (3.1 mmol)was added, and the reaction mixture was refluxed for another 8 hours. GCshowed 86% conversion, and 76% selectivity to3-isopropyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol. The mixturewas diluted with ether (20 ml) and 10% HCl (20 ml). The layers wereseparated, and the aqueous layer was extracted with ether (3×20 ml). Theether layers were combined, dried (MgSO₄), and concentrated. The crudeproduct was purified by column chromatography (SiO₂, 2% ethylacetate/hexanes) to yield 1.1 g white solid (48%). MP: 100-102° C.

Example 15 Synthesis of3-cyclopentyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol

[0063] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol (2 g,6.8 mmol), cyclopentyl methanesulfonate (6.34 mmol), scandium triflate(0.34 g, 5 mol %), and carbon tetrachloride (10 ml) was heated to refluxunder argon for 10 hours. GC showed 93% conversion and 77% selectivityto 3-cyclopentyl-5,5′,6,6′,7,7′, 8,8′-octahydro-2,2′-binaphthol. Themixture was diluted with ether (20 ml) and 10% HCl (20 ml). The layerswere separated, and the aqueous layer was extracted with ether (3×20ml). The ether layers were combined, dried (MgSO₄), and concentrated.The crude product was purified by column chromatography (SiO₂, 2% ethylacetate/hexanes) to yield 1.4 g white solid (57%). ¹H NMR (CDCl₃): 1.58(m, 14H), 2.05 (m, 6H), 2.66 (m, J=5 Hz, 4H), 3.18 (quintet, J=8 Hz,1H), 4.52 (s, 1H), 4.51 (s, 1H), 6.73 (d, J=8 Hz, 1H), 6.92 (s, 1H),6.97 (d, J=8 Hz, 1H) ppm. ¹³C NMR (CDCl₃): 22.82, 22.87, 23.01, 25.36,26.70, 26.94, 29.09, 29.20, 32.73, 32.75, 39.28, 112.73, 118.23, 119.13,128.24, 129.19, 129.85, 130.72, 133.72, 137.03, 149.14, and 151.33 ppm.

[0064] Example 16

Synthesis of 3-tert-butyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol

[0065] A mixture of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol (1.0g, 3.4 mmol), tert-butyl alcohol (1.4 g), trifluoromethanesulfonic acid(0.04 g) was dissolved in 2 ml 1,2-dichlorobenzene. The mixture washeated at 120° C. for 2.5 hours. GC showed 97% conversion to 87%mono-butylated product, and 10% bis-butylated product. The mixture wascooled, and diluted with 10 ml water and 10 ml ether. The layers wereseparated, and the organic layer was washed with sodium bicarbonatesolution, dried, and concentrated. The crude product was purified byflash column chromatography (silica gel, 2% ethyl acetate/hexanes) toyield 0.7 g of white solid.

What is claimed is:
 1. A compound of the formula

wherein: R is C₁ to C₂₀ alkyl, C₃ to C₂₀ cycloalkyl, or benzyl of theformula

 wherein each R′ is independently H, alkyl or cycloalkyl of up to 6carbons; and/or a compound of the formula

 wherein R is C₁ to C₂₀ alkyl other than methyl or t-butyl, C₃ to C₂₀cycloalkyl, or benzyl of the formula

 wherein each R′ is independently H, alkyl or cycloalkyl of up to 6carbons.
 2. A process for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol,comprising contacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol withat least one alkene or cycloalkene in the presence of an acid catalyst.3. The process of claim 2 wherein the at least one alkene or cycloalkeneis monoethylenically unsaturated and contains from 3 to 20 carbon atoms.4. The process of claim 3 wherein at least one alkene or cycloalkene isselected from the group consisting of propylene, butene, pentene,hexene, cyclopentene, and cyclohexene.
 5. The process of claim 2 whereinthe acid catalyst is selected from the group consisting of aluminumchloride, trifluoromethanesulfonic acid, tosylic acid, phosphotungsticacid, silicotungstic acid, phosphomolybdic acid, zirconium triflate,aluminum triflate, polymeric perfluorinated sulfonic acid and polymericsulfonic acid.
 6. The process of claim 5 wherein the acid catalyst isaluminum chloride, phosphotungstic acid, or phosphomolybdic acid.
 7. Theprocess of claim 6 wherein the acid catalyst is phosphotungstic acid. 8.The process of claim 2 wherein the contacting is done in the presence ofat least one solvent selected from the group consisting of nitromethane,methylene chloride, dichloroethane, chlorobenzene, dichlorobenzene, andnitrobenzene.
 9. The process of claim 2 wherein the contacting is doneat a temperature between 20° C. and 220° C.
 10. The process of claim 9wherein the temperature is between 90° C. and 180° C. and wherein the5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol is contacted with a mono-or 1,2-disubstituted alkene.
 11. The process of claim 9 wherein thetemperature is between 40° C. and 90° C. and wherein the5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol is contacted with at leastone alkene selected from the group consisting of 1,1-disubstitutedalkene, tri-substituted alkene, tetra-substituted alkene oraryl-substituted alkene.
 12. A process for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol,comprising contacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol witha benzyl halide or tertiary alkyl halide, wherein the halide is bromideor chloride, in the presence of a Lewis acid catalyst.
 13. The processof claim 12 wherein the Lewis acid catalyst is selected from the groupconsisting of aluminum chloride, zinc chloride, boron trichloride,SnCl₄, SbCl₅, and ZrCl₄.
 14. The process of claim 13 wherein the Lewisacid catalyst is zinc chloride.
 15. A process for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or3,3′-dialkylated-5,5′, 6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol,comprising contacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol withan alkyl sulfonate, alkyl triflate, alkyl p-toluenesulfonate, or alkylbenzenesulfonate, in the presence of an acid catalyst selected from thegroup consisting of aluminum chloride, tosylic acid, phosphotungsticacid, silicotungstic acid, phosphomolybdic acid,trifluoromethanesulfonic acid and a rare earth metal triflate selectedfrom the group consisting of scandium trifluoromethanesulfonate,ytterbium trifluoromethanesulfonate, and lanthanumtrifluoromethanesulfonate.
 16. The process of claim 15 in which thealkyl sulfonate is of the formula A-SO₃—B, wherein A is C₁ to C₈ alkyl,C₁ to C₈ fluorinated alkyl, C₆ to C₁₀ aryl, or C₆ to C₁₀ fluorinatedaryl; and B is C₁ to C₂₀ alkyl.
 17. A process for making3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol,comprising contacting 5,5′,6,6′,7,7′,8,81-octahydro-2,2′-binaphthol witha benzyl, secondary or tertiary alcohol containing fro 3 to 20 carbonatoms, in the presence of an acid catalyst selected from the groupconsisting of trifluoromethanesulfonic acid, sulfuric acid, HF,phosphoric acid, and aluminum chloride.
 18. A compound of the formula

wherein: R is H; and R′ is ethyl, C₃ to C₆ secondary, tertiary, orcyclic alkyl; or a compound of the above formula wherein R and R′ arethe same and are selected from the group consisting of ethyl, C₃ to C₆secondary or cyclic alkyl.
 19. A compound of claim 18 wherein R and R′are the same are selected from the group consisting of ethyl, isopropyl,cyclopentyl, and cyclohexyl.